CN102826569A - Preparation method for mesoporous ZSM-5 zeolite molecular sieve - Google Patents
Preparation method for mesoporous ZSM-5 zeolite molecular sieve Download PDFInfo
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- CN102826569A CN102826569A CN2012102879141A CN201210287914A CN102826569A CN 102826569 A CN102826569 A CN 102826569A CN 2012102879141 A CN2012102879141 A CN 2012102879141A CN 201210287914 A CN201210287914 A CN 201210287914A CN 102826569 A CN102826569 A CN 102826569A
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Abstract
The invention discloses a preparation method for a mesoporous ZSM-5 zeolite molecular sieve. The mesoporous zeolite molecular sieve with ZSM-5 microporous crystalline pore walls is prepared by using tetraethoxysilane as a silicon source, sodium metaaluminate as an aluminum source and a difunctional triammonio quaternary ammonium salt cationic surfactant as a template through a hydrothermal synthesis process under an alkaline condition. According to the invention, the quaternary ammonium surfactant is used as a ZSM-5 zeolite structure directing agent and generates micropores, and aggregation of long hydrophobic alkyl groups at two ends of the surfactant forms meso pores. The method provided by the invention effectively changes an amorphous pore wall structure of traditional mesoporous materials and allows the ZSM-5 zeolite molecular sieve to have crystalline pore walls, which enables acidity and hydrothermal stability of mesoporous materials to be greatly improved; the prepared mesoporous ZSM-5 zeolite molecular sieve has a unique mesoporous/microporous multiple pore structure, so defects of a single pore structure are avoided, mass transfer efficiency is improved, and the ZSM-5 zeolite molecular sieve has a wide application prospect in aspects like macro-molecular catalysis, adsorption, separation, etc.
Description
Technical field
The invention belongs to technical field of inorganic material, relate to a kind of mesoporous zeolite material and preparation method thereof, be specifically related to a kind of method of utilizing three ammonium quaternary surfactants to have the mesoporous zeolite molecular sieve of ZSM-5 crystalline zeolite hole wall structure for the template preparation.
Background technology
ZSM-5 is the micro porous molecular sieve with MFI structure, because its unique pore passage structure, and distinctive shape selective, advantages such as acid strong and good hydrothermal stability are widely used as fields such as refining of petroleum, Coal Chemical Industry and fine chemistry industry.But because the aperture of micro porous molecular sieve is less; Macromole gets into the duct difficulty on the one hand; The macromole diffusional resistance that behind its vestibule internal adsorption, forms on the other hand can not be overflowed more greatly fast; Cause the generation of side reaction, so there is certain limitation in micro porous molecular sieve in relating to macromolecular catalyzed reaction.
In order to solve macromole spreads difficulty in micro-pore zeolite problem; Developed mesopore molecular sieve with 2 ~ 30nm adjustable aperture; Like [Kresge C.T. Leonowicz M.E. Roth W.J. Vartuli J.C. Beck J.S. Ordered mesoporous molecular sieves synthesized by a liquid crystal template mechanism. Nature such as Kresge; 1992; (359): 710-712] prepared M41s type molecular sieve; [Zhao D.Y. Feng J.L. Huo Q.S. Melosh N. Fredrickson G.H. Chmelka B.F. Stucky G.D. Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores. Science such as Zhao; 1998; (279): 548-552] prepared SBA-n type molecular sieve; And the MSU-x type molecular sieve of Bagshaw etc. [Bagshaw S.A. Pouzet E. Pinnavaia T.J. Templating of mesoporous molecular sieves by nonionic polyethylene oxide surfactants. Science, 1995, (269): 1242-1244] preparation.The aperture of this type mesoporous material is a kind of porous material with large surface area between micropore and 2～50nm macropore.But, cause its acidity and hydrothermal stability relatively low, so mesoporous material has received very big restriction in practical application because the hole wall of mesopore molecular sieve is in metamict.
The ideal method is to make material when keeping central hole structure, synthesizes the mesoporous of existing larger aperture structure, has the strongly-acid of zeolite type hole wall structure, the mesoporous zeolite of high hydrothermal stability again.The high-specific surface area of the acidity that this material is stronger with micro porous molecular sieve and good hydrothermal stability and mesopore molecular sieve and superior diffusion organically combine; Overcome micro porous molecular sieve and mesopore molecular sieve limitation separately; Make the two mutual supplement with each other's advantages, having broad application prospects aspect macromolecular absorption and the catalytic conversion of heavy oil.As: people [Liu Y. Zhang W.Z. Pinnavaia T.J. Steam-Stable MSU-S Aluminosilicate Mesostructures Assembled from Zeolite ZSM-5 and Zeolite Beta Seeds. Angew.Chem.Int.Ed such as Liu Yu; 2001, (40): 1255-1258] utilize and preset the crystal seed that crystal seed method will have MFI and BEA primary structure units and under 150 ℃ of conditions, be assembled into meso-porous molecular sieve material with hydrothermal stability with CTAB; People [Huang L.M. Guo W.P. Deng P. Xue Z.Y. Li Q.Z. Investigation of Synthesizing MCM-41/ZSM-5 Composites. J.Phys.Chem.B such as Huang Limin; 2000; (104): 2817-2823] adopt two step crystallization methods at first to synthesize mesoporous MCM-41 material; And then, prepared the MCM-41/ZSM-5 composite molecular screen with the hole wall of zeolite structured directed agents recrystallization mesoporous material; People [Xu H.Y. Guan J.Q. Wu S.J. Kan Q.B. Synthesis of Beta/MCM-41 composite molecular sieve with high hydrothermal stability in static and stirred condition. J. Colloid Interface Sci such as Xu Haiyan; 2009, (329): 346-350] utilize the hydrolysis structural unit of CTAB assembling zeolite under strong alkaline condition to prepare the Beta/MCM-41 composite molecular screen.Yet the hole wall of these composite molecular screens is still unbodied in essence, does not fundamentally improve the acidity and the hydrothermal stability of mesoporous material.
Summary of the invention
The objective of the invention is to above-mentioned existing in prior technology problem and defective; A kind of preparation method of mesoporous ZSM-5 zeolite molecular sieve is provided; Adopting single three ammonium head quaternary surfactants is that template prepares existing mesopore; The crystalline-state mesoporous ZSM-5 zeolite molecular sieve that ZSM-5 micro-pore zeolite hole wall is arranged again, the percent crystallinity of raising mesopore molecular sieve hole wall structure has the potential using value in petrochemical complex and environmental protection field.
The present invention adopts hydrothermal synthesis method to contain al compsn, to contain silicon components and highly basic is raw material, utilize three ammonium quaternary surfactants for the template self-assembly forms mesoporous ZSM-5 zeolite, template is removed in roasting after the crystallization, obtains mesoporous ZSM-5 zeolite molecular sieve.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of preparation method of mesoporous ZSM-5 zeolite molecular sieve as the silicon source, as the aluminium source, prepares mesoporous ZSM-5 zeolite molecular sieve with difunctional three ammonium quaternary surfactants as template with sodium metaaluminate with tetraethoxy, may further comprise the steps:
(1) with difunctional three ammonium quaternary surfactants, second alcohol and water according to mol ratio (1 ~ 1.3): (80 ~ 104): (856 ~ 1316) mix; Form A liquid; With sodium metaaluminate, sodium hydroxide and water according to mol ratio (1 ~ 1.5): (7.5 ~ 11.3): mix (463 ~ 827), obtains B liquid;
(2) under stirring condition, A liquid is joined in the B liquid, form C liquid;
(3) while stirring tetraethoxy or water glass slowly are added drop-wise in the C liquid at 50～60 ℃, form gel, continue to stir 4～6 hours, and 40～60 ℃ of following ageings 8～12 hours;
(4) with the product of step (3) in 140～150 ℃ of sealing crystallization 96～120 hours, washing, filter, dry back in 500～550 ℃ of calcinings 5 ~ 6 hours, obtains mesoporous ZSM-5 zeolite molecular sieve in air.
The quality group of said sodium metaaluminate becomes: 44.7% sodium oxide, 52% aluminum oxide.
The mol ratio of said each material is: tetraethoxy: sodium metaaluminate: sodium hydroxide: difunctional three ammonium quaternary surfactants: ethanol: water=1: (0.04～0.07): (0.28～0.39): (0.04～0.06): 4:72.
Be preferably: tetraethoxy or water glass: sodium metaaluminate: sodium hydroxide: difunctional three ammonium quaternary surfactants: ethanol: water=1:0.05:0.38:0.05:4:72.
Said difunctional three ammonium quaternary surfactants are pressed document [Na K. Choi M. Park W. Sakamoto Y. Terasaki O. Ryoo R. Pillared MFI Zeolite Nanosheets of a Single-Unit-Cell Thickness. J. Am. Chem. Soc; 2010; (132): 4169-4177 method] is synthetic, and concrete steps are following:
(1) with the N of 0.0113mol; 1 of N-dimethyl--1-hexadecylamine and 0.113mol, 6-dibromo-hexane are dissolved in toluene and the acetonitrile volume ratio is in the 50ml mixing solutions of 1:1, refluxes while stirring 8 hours in 65 ℃; Cool to room temperature; Volatilization removes and desolvates, and the deposition that obtains is with ether washing, filtration, vacuum-drying, and the solid that obtains is designated as [C
16H
33– N
+(CH
3)
2– C
6H
12– Br] Br
-
(2) with the 1-bromine n-Hexadecane of 0.01mol and the N of 0.1mol, N, N'; N'-tetramethyl--1,6-hexanediamine are dissolved in toluene and the acetonitrile volume ratio is in the 50ml mixing solutions of 1:1, refluxes while stirring 8 hours in 65 ℃; Cool to room temperature; Volatilization removes and desolvates, and the deposition that obtains is with ether washing, filtration, vacuum-drying, and the solid that obtains is designated as [C
16H
33– N
+(CH
3)
2– C
6H
12– N (CH
3)
2] Br
-
(3) with [C of 0.005mol
16H
33– N
+(CH
3)
2– C
6H
12– Br] Br
-[C with 0.005mol
16H
33– N
+(CH
3)
2– C
6H
12– N (CH
3)
2] Br
-Be dissolved in the acetonitrile solution of 40ml, refluxed while stirring 8 hours in 75 ℃, cool to room temperature, volatilization removes and desolvates, and the deposition that obtains promptly obtains difunctional three ammonium head quaternary surfactants with ether washing, filtration, vacuum-drying.
The present invention compared with prior art has the following advantages and beneficial effect:
(1) the present invention utilize three ammonium quaternary surfactants for the template self-assembly forms mesoporous ZSM-5 zeolite; Because the ammonium functional group in the surfactant structure has synthesized the microvoid structure of crystallization as effective ZSM-5 structure directing agent, the gathering of the long alkyl chain length in two ends has then formed mesoporous;
(2) (be called for short: TEOS), sodium metaaluminate and sodium hydroxide/potassium is as raw material, adopts hydrothermal synthesis method, raw material is easy to get inexpensive, and technology is simple, and cost is low with tetraethoxy in the present invention;
(3) the existing mesopore of crystalline-state mesoporous ZSM-5 zeolite molecular sieve of the present invention's preparation has ZSM-5 micro-pore zeolite hole wall again, has improved the percent crystallinity of mesopore molecular sieve hole wall structure, in petrochemical complex and environmental protection field the potential using value is arranged.
Description of drawings
Fig. 1 is the X-ray diffractogram of the mesoporous ZSM-5 zeolite molecular sieve of the embodiment of the invention 4 preparations, and wherein (a) is the X-ray diffractogram of low angle diffraction zone, (b) is high angle diffraction zone and the correlated X-ray diffractogram of common ZSM-5 zeolite.
Fig. 2 is the transmission electron microscope picture of the mesoporous ZSM-5 zeolite molecular sieve of the embodiment of the invention 4 preparations.
Fig. 3 is the mesoporous ZSM-5 zeolite molecular sieve of the embodiment of the invention 4 preparation and the nitrogen adsorption-desorption isotherm of common ZSM-5 zeolite.
Fig. 4 is the mesoporous ZSM-5 zeolite molecular sieve pore size distribution curve of the embodiment of the invention 4 preparations.
Embodiment
Below in conjunction with specific embodiment the present invention is further described, but the scope that the present invention requires to protect is not limited thereto.
The medicine and the tetraethoxy of preparation three ammonium quaternary surfactants are all purchased in lark prestige scientific & technical corporation among the embodiment, and sodium metaaluminate is purchased in Aladdin reagent (Shanghai) Co., Ltd., and all the other raw materials adopt the analytical pure medicine.
Embodiment 1
(1) 1.189g (0.0012mol) three ammonium quaternary surfactants and 5.6mL ethanol are dissolved in the 12mL water; Form A liquid; 0.111g (0.0012mol) sodium metaaluminate and 0.36g (0.009mol) sodium hydroxide are dissolved in the 19.5mL water, obtain B liquid;
(2) under stirring condition, A liquid is joined in the B liquid, form C liquid;
(3) under 60 ℃ of magnetic agitation, 5.077g (0.024mol) tetraethoxy slowly is added drop-wise in the C liquid, form gel, continue to stir 6 hours, and 50 ℃ of following ageings 12 hours;
(4) product of step (3) is packed in the crystallization still of sealing, 150 ℃ of following crystallization 120 hours, washing, filter, dry back removed template in 6 hours in 550 ℃ of calcinings in air, obtain mesoporous ZSM-5 zeolite molecular sieve.
Embodiment 2
(1) 0.797g (0.0008mol) three ammonium quaternary surfactants and 3.8mL ethanol are dissolved in the 9mL water, form A liquid, 0.075g (0.0008mol) sodium metaaluminate and 0.24g (0.006mol) sodium hydroxide are dissolved in the 12mL water, obtain B liquid;
(2) under stirring condition, A liquid is joined in the B liquid, form C liquid;
(3) under 60 ℃ of magnetic agitation, 3.418g (0.016mol) tetraethoxy slowly is added drop-wise in the C liquid, form gel, continue to stir 6 hours, and 60 ℃ of following ageings 10 hours;
(4) product of step (3) is packed in the crystallization still of sealing, 140 ℃ of following crystallization 96 hours, washing, filter, dry back removed template in 5 hours in 550 ℃ of calcinings in air, obtain mesoporous ZSM-5 zeolite molecular sieve.
Embodiment 3
(1) 1.487g (0.0015mol) three ammonium quaternary surfactants and 7mL ethanol are dissolved in the 18mL water, form A liquid, 0.139g (0.0015mol) sodium metaaluminate and 0.44g (0.011mol) sodium hydroxide are dissolved in the 21.4mL water, obtain B liquid;
(2) under stirring condition, A liquid is joined in the B liquid, form C liquid;
(3) under 60 ℃ of magnetic agitation, 6.346g (0.03mol) tetraethoxy slowly is added drop-wise in the C liquid, form gel, continue to stir 6 hours, and 50 ℃ of following ageings 12 hours;
(4) product of step (3) is packed in the crystallization still of sealing, 140 ℃ of following crystallization 120 hours, washing, filter, dry back removed template in 6 hours in 550 ℃ of calcinings in air, obtain mesoporous ZSM-5 zeolite molecular sieve.
Embodiment 4
(1) 0.595g (0.0006mol) three ammonium quaternary surfactants and 2.8mL ethanol are dissolved in the 8mL water; Form A liquid; 0.056g (0.0006mol) sodium metaaluminate and 0.184g (0.0046mol) sodium hydroxide are dissolved in the 7.8mL water, obtain B liquid;
(2) under stirring condition, A liquid is joined in the B liquid, form C liquid;
(3) under 60 ℃ of magnetic agitation, 2.539g (0.012mol) tetraethoxy slowly is added drop-wise in the C liquid, form gel, continue to stir 5 hours, and 40 ℃ of following ageings 8 hours;
(4) product of step (3) is packed in the crystallization still of sealing, 150 ℃ of following crystallization 110 hours, washing, filter, dry back removed template in 5 hours in 550 ℃ of calcinings in air, obtain mesoporous ZSM-5 zeolite molecular sieve.
Mesoporous ZSM-5 zeolite molecular sieve to embodiment 4 preparations carries out structural characterization.
As shown in Figure 1, mesoporous ZSM-5 zeolite molecular sieve of the present invention has presented three characteristic diffraction peaks in the low angle diffraction zone, belong to 100,110 and 310 crystal face diffraction successively, and is corresponding
dValue does
d=5.29,2.95,1.46nm, this interpret sample has the meso-hole structure that two dimension six sides arrange, and is similar to MCM-41; And in the high angle diffraction zone, sample has presented the characteristic diffraction peak of the crystalline microporous zeolite of ZSM-5.
Adopt JEM-2100HR type transmission electron microscope (JEOL of electronics corporation, Japan) that product is characterized.As shown in Figure 2, mesoporous ZSM-5 zeolite molecular sieve of the present invention has presented the mesoporous wall structure of crystallization.
Adopt ASAP 2010 type N
2Adsorption analysis appearance (Merck & Co., Inc, the U.S.) is analyzed the pore structure of product.As shown in Figure 3, mesoporous ZSM-5 zeolite molecular sieve of the present invention has shown IV type adsorption isothermal line.0.0＜
P/P 0 ＜0.1 low
P/P 0 The district, adsorptive capacity with
P/P 0 Increase and sharply increase, this is because N
2Filling in the micropore district; 0.6＜
P/P 0 The desorption hysteresis loop appears in＜0.8 district, explains to exist mesoporously in the product, belongs to N
2Capillary condensation phenomenon in mesoporous; Greater than
P/P 0 =0.8 zone, adsorptive capacity rises again, is because N
2Absorption in the macropore that between particle, forms.
The pore size distribution curve of Fig. 4 for obtaining according to desorption BJH Model Calculation explains that there is narrower mesoporous pore size distribution in mesoporous ZSM-5 zeolite molecular sieve of the present invention, and its mean pore size is 3.6nm.
Claims (5)
1. the preparation method of a mesoporous ZSM-5 zeolite molecular sieve; As the silicon source, as the aluminium source, prepare mesoporous ZSM-5 zeolite molecular sieve as template with tetraethoxy with difunctional three ammonium quaternary surfactants with sodium metaaluminate; It is characterized in that, may further comprise the steps:
(1) with difunctional three ammonium quaternary surfactants, second alcohol and water according to mol ratio (1 ~ 1.3): (80 ~ 104): (856 ~ 1316) mix; Form A liquid; With sodium metaaluminate, sodium hydroxide and water according to mol ratio (1 ~ 1.5): (7.5 ~ 11.3): mix (463 ~ 827), obtains B liquid;
(2) under stirring condition, A liquid is joined in the B liquid, form C liquid;
(3) under 50～60 ℃, while stirring tetraethoxy slowly is added drop-wise in the C liquid, forms gel, continue to stir 4～6 hours, and 40～60 ℃ of following ageings 8～12 hours;
(4) with the product of step (3) in 140～150 ℃ of sealing crystallization 96～120 hours, washing, filter, dry back in 500～550 ℃ of calcinings 5 ~ 6 hours, obtains mesoporous ZSM-5 zeolite molecular sieve in air.
2. preparation method according to claim 1 is characterized in that, the chain alkyl carbon atom number of said difunctional three ammonium quaternary surfactants is 16.
3. preparation method according to claim 2 is characterized in that, the quality group of said sodium metaaluminate becomes: 44.7% sodium oxide, 52% aluminum oxide.
4. preparation method according to claim 3; It is characterized in that the mol ratio of said each material is: tetraethoxy: sodium metaaluminate: sodium hydroxide: difunctional three ammonium quaternary surfactants: ethanol: water=1: (0.04～0.07): (0.28～0.39): (0.04～0.06): 4:72.
5. according to the described preparation method of one of claim 1 ~ 4, it is characterized in that the aperture of the meso-hole structure of said mesoporous ZSM-5 zeolite molecular sieve is 2.4～4.8nm.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229827A (en) * | 2014-08-07 | 2014-12-24 | 华南理工大学 | Mesoporous-microporous dual-porous ZSM-5 molecular sieve as well as preparation method and application thereof |
| CN104340991A (en) * | 2013-07-29 | 2015-02-11 | 中国科学院大连化学物理研究所 | Method for preparing ZSM-5 zeolite molecular sieve, product and purpose thereof |
| CN106830001A (en) * | 2017-03-14 | 2017-06-13 | 中国矿业大学 | A kind of synthetic method of the molecular sieves of c axial directions Zn ZSM 5 with meso-hole structure |
| CN107128947A (en) * | 2017-06-30 | 2017-09-05 | 华南理工大学 | A kind of preparation method of the middle zeolite molecular sieves of micro-diplopore ZSM 5 |
| CN108328625A (en) * | 2018-01-22 | 2018-07-27 | 哈尔滨工业大学 | A kind of preparation method of hollow multi-stage porous ZSM-5 molecular sieve |
| CN108620116A (en) * | 2018-05-24 | 2018-10-09 | 南京大学盐城环保技术与工程研究院 | A kind of manganese, titanium binary load nano zeolite composite catalyzing material and its application |
| CN110330030A (en) * | 2019-07-31 | 2019-10-15 | 山东齐鲁华信实业股份有限公司 | The production method of type molecular sieve ZSM-5 is selected with the production of low Crater corrosion sodium metaaluminate |
| CN112585093A (en) * | 2018-08-27 | 2021-03-30 | 埃克森美孚研究工程公司 | Molecular sieves and methods of making molecular sieves |
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| CN104340991B (en) * | 2013-07-29 | 2016-08-10 | 中国科学院大连化学物理研究所 | Method preparing ZSM-5 zeolite molecular sieve and products thereof and purposes |
| CN104229827A (en) * | 2014-08-07 | 2014-12-24 | 华南理工大学 | Mesoporous-microporous dual-porous ZSM-5 molecular sieve as well as preparation method and application thereof |
| CN106830001A (en) * | 2017-03-14 | 2017-06-13 | 中国矿业大学 | A kind of synthetic method of the molecular sieves of c axial directions Zn ZSM 5 with meso-hole structure |
| CN107128947A (en) * | 2017-06-30 | 2017-09-05 | 华南理工大学 | A kind of preparation method of the middle zeolite molecular sieves of micro-diplopore ZSM 5 |
| CN108328625A (en) * | 2018-01-22 | 2018-07-27 | 哈尔滨工业大学 | A kind of preparation method of hollow multi-stage porous ZSM-5 molecular sieve |
| CN108328625B (en) * | 2018-01-22 | 2021-07-02 | 哈尔滨工业大学 | Preparation method of hollow hierarchical pore ZSM-5 molecular sieve |
| CN108620116A (en) * | 2018-05-24 | 2018-10-09 | 南京大学盐城环保技术与工程研究院 | A kind of manganese, titanium binary load nano zeolite composite catalyzing material and its application |
| CN108620116B (en) * | 2018-05-24 | 2021-01-19 | 南京大学盐城环保技术与工程研究院 | Manganese-titanium binary loaded nano zeolite composite catalytic material and application thereof |
| CN112585093A (en) * | 2018-08-27 | 2021-03-30 | 埃克森美孚研究工程公司 | Molecular sieves and methods of making molecular sieves |
| CN110330030A (en) * | 2019-07-31 | 2019-10-15 | 山东齐鲁华信实业股份有限公司 | The production method of type molecular sieve ZSM-5 is selected with the production of low Crater corrosion sodium metaaluminate |
| CN110330030B (en) * | 2019-07-31 | 2022-12-09 | 山东齐鲁华信实业股份有限公司 | Production method for producing selective molecular sieve ZSM-5 by using low caustic ratio sodium metaaluminate |
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Application publication date: 20121219 |